Energy conversion and reaction system and method

ABSTRACT

A system is described that is capable of operating as an energy conversion system that functions as a fuel cell and generates electrical current from a fuel or fuels, or as a reactor for conversion of starter materials into more complex molecules through ion-ion and ion-molecules and which may preferably be adapted to operate as a gas to liquid (GTL) process. The system ionises at least one fuel or starter material and manipulates, selects and transports ions for reaction by means of suitable electrostatic or electrodynamic ion guides, filters or drift tubes. The system of the present application replaces the electrolyte, catalyst and/or membrane found in classic fuel cells or GTL processes with an electrostatic or electrodynamic ion manipulation region such as an ion guide, analyser, drift tube or filter.

FIELD OF THE APPLICATION

The present application relates to conversion of gas into electricalpower or liquid(s) by means of ionic reactions in the gas phase. Thepresent application concerns a technology that may be operated as ameans of producing electric power or liquid product(s) from at least onegaseous input stream. An apparatus based on this technology is describedthat may function as a fuel cell and as a gas to liquid (GTL) conversionsystem.

BACKGROUND

Fuel cells convert fuel from a fuel reservoir directly into electricalcurrent. GTL plants convert natural gases such as methane into liquidfuels such as methanol or ethanol that can be easily stored andtransported.

A critical feature of existing fuel cell and gas to liquid processes isthe requirement for a catalyst and, in the case of fuel cells, anelectrolyte. In most modern fuel cells the electrolyte is an ionicmembrane. These features require careful engineering and selection ofmaterials. Frequently precious or rare earth metals are utilised,contributing to the expense of the device. The use of precious metals ascatalytic materials, and the price volatility of commodities, can makefuel cells and GTL technologies uneconomic. The reliability andlongevity of these devices is limited by gradual deterioration of theeffectiveness of catalytic materials due to mechanisms such as coating,deposition and oxidation. The overall efficiency of the cell or GTLprocess falls over time unless expensive materials are used. Similarlymembranes and electrolytes exploited in fuel cells gradually deteriorateover time due to changes in their chemical composition and because ofcrystallisation, oxidation and coating with impermeable films ordielectric layers.

Patent document U.S. Pat. No. 6,924,401 B2 describes a plasma reformingprocess relying on random collisions of neutral (uncharged) moleculesfrom starter materials (i.e. Oxygen, Methane) with ions and electrons ina local plasma, and their subsequent ionisation and reaction to producea small quantity of Methanol. These reactions are unguided andconsequently the overall yield is limited by the number of moleculesthat can intersect and collide in the small volume of the plasma, andthen only a minority follow a reaction pathway that results in methanol.

Other examples of plasma reforming systems and methods are found in thefollowing documents: “A review of direct methane conversion to methanolby dielectric barrier discharge” from Antonius Indarto, in IEEETransactions on dielectrics and electrical insulation, September 2008;JP2004285187A; JPH10182521A; “Single Step oxidation of methane tomethanol—towards better understanding”, P. Khirsariya, R. K. Mewada,Procedia Engineering 51 (2013) 409-415; “The future of GTL—Why smallerscale GTL still makes sense in a low-oil price world”, Jeff McDaniel,GTL Technology Forum, Houston, Jul. 29-30th 2015; “The impact ofcatalyst-reactor performance on commercial GTL plant design andoperation”, Dr. Paul F. Schubert & Andre P. Steynberg, GTL TechnologyForum, Houston, Jul. 29-30th 2015; WO2004024280A2, WO2010041113A1 andWO2013020042A1, the entire contents of which are herein incorporated byreference.

SUMMARY

A device and method are described that eliminates the conventionalrequirement for electrolyte and catalyst in a fuel cell or GTL device.

There is provided an energy conversion device comprising at least onefirst ionisation region and at least one second ionisation region togenerate ions from respective input streams of starting material; and atleast one ion manipulation region for conveying generated ions from oneor both of the at least one first ionisation region and the at least onesecond ionisation region to facilitate a reaction between the generatedions of the respective streams, wherein the ion manipulation regioncomprises at least one ion guide for filtering the generated ions.

In a particular case, the one or both of the at least one firstionisation region and the at least one second ionisation region areconfigured to provide a soft ionization of the starting material.

In another particular case, the soft ionisation is provided by one ofthe following techniques: chemical ionisation, electrospray ionisation,microspray, nanospray ionisation, photoionisation, laser ionisation,field effect ionisation, electron impact, low temperature plasmaionisation, glow discharge ionisation, secondary ionisation, chargetransfer and corona discharge ionisation.

In another particular case, the at least one ion guide comprises one ofthe following: mass analyser, ion mobility spectrometer.

In another particular case, the energy conversion device employs lowloss ion optics for coupling the at least one ion manipulation region tothe at least one first ionisation region and the at least one secondionisation region.

In another particular case, the low loss optics comprises one of thefollowing: RF-only ion guide, electrostatic lenses, Brubaker lens,einzel lens, stacked rings, cylinder lens or ion funnel, pre-filters,hexapoles, quadrupoles, octopoles, ion mobility, drift tubes, travellingwave ion guides, stacked ring ion guides, bunching optics or Starkdecelerators.

In another particular case, the energy conversion device comprises inthe ion manipulation region a trap to collect and filter the generatedions.

In another particular case, the trap comprises one of the following:quadrupole, rectilinear, linear, toroidal or cylindrical ion trap.

In another particular case, the at least one ion guide further comprisesan ion filter for selectively transferring the generated ions accordingto one or both of their mass to charge ratio and ion mobility.

In another particular case, the at least one ion manipulation region theat least one first ionisation region and the at least one secondionisation region are constructed from microfabricated components.

In another particular case, the at least one first ionisation region andthe at least one second ionisation region have opposite polarities.

There is also provided an energy conversion system comprising an arrayof devices as described above.

There is also provided a Gas To Liquid device comprising a device asdescribed above.

In a particular case of the Gas To Liquid device, the starting materialfor the at least one first ionisation region is one of the following:methane, hydrogen, ethane, butane, pentane, methanol or ethanol and thestarting material for the at least one second ionisation region is oneof the following: oxygen, air, water.

There is also provided a fuel cell comprising a device as describedabove.

In a particular case of the fuel cell, the starting material for the atleast one first ionisation region is one of the following: hydrogen orpositive or protonated ions and the starting material for the at leastone second ionisation region is oxygen.

There is also provided a method for energy conversion comprising:generating ions from respective input streams of starting material in atleast one first ionisation region and at least one second ionisationregion; conveying generated ions in at least one ion manipulation regionfrom one or both of the at least one first ionisation region and the atleast one second ionisation region to facilitate a reaction between thegenerated ions of the respective streams; wherein the method furthercomprises filtering the generated ions in at least one ion guide of theion manipulation region.

In a particular case, the method further comprises selecting thegenerated ions in the at least one ion manipulation region according toone or both of their mass to charge ratio and ion mobility.

In a particular case, generating the ions comprises a soft ionization ofthe starting material in the at least one first ionisation region andthe at least one second ionisation region.

In a particular case, the soft ionisation comprises one of thefollowing: chemical ionisation, electrospray ionisation, microspray,nanospray ionisation, photoionisation, laser ionisation, field effectionisation, electron impact, low temperature plasma ionisation, glowdischarge ionisation, secondary ionisation, charge transfer and coronadischarge ionisation.

In a particular case, the at least one ion guide comprises one of thefollowing: mass analyser, ion mobility spectrometer.

In a particular case, the method further comprises coupling the at leastone ion manipulation region to the at least one first ionisation regionand the at least one second ionisation region with low loss ion optics.

In a particular case, the method further comprises collecting andfiltering the generated ions in a trap of the ion manipulation region.

In a particular case, the method further comprises selectivelytransferring the generated ions according to one or both of their massto charge ratio and ion mobility.

In a particular case, the at least one first ionisation region and theat least one second ionisation region have opposite polarities.

The present application is efficient and readily scalable. An advantageof the device of the present teaching includes, for example, but is notlimited to trapping positive and negative ions in the same volume or inclose proximity, i.e. in a sub millimetre range, in adjacent ion guidesfor reaction in an intermediate region. With the device of the presentteaching, a very high charge density, of 10⁶ ions or greater, may beachieved increasing yield and throughput, e.g. using quadrupole ionguides rather than traps.

The use of an ion guide permits the separation of ions from neutralparticles, enriching the input stream. The presence of other neutralparticles may reduce efficiency by providing alternative and lessdesirable reaction pathways, reducing the overall throughput. Using theion guide to separate ions from neutrals enriches the reaction pathwayand discriminates in favour of the reactants so that only the ionsproceed to the reaction region, and neutral molecules are pumped away.Furthermore, the selection of ions by their mass to charge ratio or ionmobility permits greater specificity in reactions by combining desiredmolecules only, and rejecting others. Hence the device of the presentteaching provides a higher selectivity than plasma reforming permittingproduction of methanol and other products without catalysts in ambientconditions.

In the present application, ions are generated separately and thenextracted from the surrounding neutrals by means of ion guides, and thentransported as an enriched, reactive, ionic stream to the a region wherethey are focussed, combining to generate the desired reaction products.If the starter ions are selected by mass to charge or mobility, theoverall yield is increased further. The reacting ions are focussed andcombined into an undiluted stream by means of the ion guides.

The technology of the present application does not suffer from thedisadvantages of membranes or catalysts outlined above, and may beconstructed from commonplace materials such as stainless steel and cheapceramic insulators.

Therefore, the benefits of the technology of the present applicationinclude low materials costs, reliability, stability and longevity.

At the heart of the chemical reactions occurring in processes such asthe electrical fuel cells and GTL is chemical reduction and oxidation.Chemical oxidation results in the loss of electrons, whereas chemicalreduction results in a gain of electrons. Together these processes areknown as ‘redox’ reactions. These reactions may be promoted by presenceof certain reactants, catalysts and accelerated by heat, pressure andthe adjustment of composition and flow rates. Intermediate compounds arefrequently formed before the reaction products. In the case of GTLprocesses ‘syngas’, an intermediate mixture of carbon monoxide,hydrogen, and carbon dioxide is formed in a high temperaturetransformation of methane prior to the formation of methanol. In thedevice of the present application, chemical ionisation is exploited topromote oxidation and reduction in positive and negative ionisationregions respectively. The ionisation products are then transferred forreaction together to form the desired reaction products by means of anion transportation device, or ion guide. In this way the use ofionisation regions displaces the electrolyte and catalysts of a fuelcell, and the ion guide supersedes the membrane. Similarly, theutilisation of ionisation regions overcomes the necessity for uniquereaction conditions in GTL plant, such as elevated temperature, pressureand catalysts, whereas the ion guide supplants catalysts. If thetechnology of the present application can be constructed from widelyavailable materials such as stainless steel and standard ceramicinsulators, the significant advantages in cost and reliability may beachieved as asserted above.

Advantages of the system of the present application include: its abilityto start from cold, without the need to head catalysts or reactionvessels to some optimum temperature; that it produces no heating anddoes not require intricate heat transfer features such as radiators orcoolant flow through micro-channels; that it runs off humid air; it runsoff a variety of fuels comprising a range of hydrocarbons; that there isno liquid electrolyte but rather a selective means of transfer; that theabsence of an electrolyte means it cannot clog with carbon; that it isscalable; that no rare earth or precious metals are required; that ithas no moving parts and that the widespread availability of strandedgas, which is otherwise flared, means that a substantial marketopportunity exists for a reliable, cost effective means of generatingelectric power or liquids from natural gas both offshore and onshore.

Ionisation is a process whereby neutral molecules can gain or losecharge. Ionisation sources typically impart or draw electrons frommolecules in the presence of electrodes and strong electrical fields.There are many ionisation sources: the list of ionisation sourcesincludes electron ionisation, photoionization, chemical ionisation,corona discharge, radioactive ionisation, electrospray ionisation,electrosonic ionisation and thermal ionisation. Some of these ionisationtechniques operate in vacuum conditions while other ionisationtechniques are possible under ambient condition. These are known asatmospheric pressure or ambient ionisation and include electrospray,microspray, nanospray and atmospheric pressure chemical ionizationsources. The ionisation technique is typically selected based on thechemistry of the molecules to be ionised. For example, polar moleculesionise well in electrospray sources, whereas non-polar molecules such ashydrocarbons ionise in chemical ionisation sources. Some ionisationtechniques such as electron ionisation are considered to be ‘hard’ sincethey result in fragmentation of molecules during ionisation. Others aredescribed as ‘soft’ since the molecule is largely preserved and aso-called molecular or pseudo-molecular ion is formed, preserving mostof the chemical bonds in the group. A further category of ionisationtechniques relies on the creation of secondary ions from primary ionsgenerated in a source. The primary ions are known to ionise othermolecular species using processes such as change transfer ordissociation. An example under vacuum conditions is chemical ionisation,which utilises an electron ionisation source in a higher pressure regionto generate primary ions from a supply of known chemical known as anadduct. These primary ions then react with specific analyte molecules ina second region to generate detectable product ions. Other examples thatoccur under ambient conditions include secondary electrospray ionisationand direct electrospray ionisation.

In the technology of the present application an ionisation region isconstructed. The ionisation region incorporates an ionisation source.The ionisation source is used to generate ions from an input stream ofstarting material. The input stream could be a fuel such as methanol,ethanol, methane or hydrogen in the case of a fuel cell, or methane inthe GTL plant instance. The ionization region is preferably operated atambient conditions (e.g. atmospheric pressure and temperature) forreasons of throughput, cost, complexity and efficiency. Examples ofatmospheric pressure ionisation techniques include electrosprayionisation, microspray, nanospray ionisation, photoionisation, laserionisation, field effect ionisation, electron impact, glow dischargeionisation and corona discharge ionisation or any other ionisationtechnique that generates ions for manipulation within the device of thepresent application. The ionisation region is operated to generate ionsfrom the input stream.

The present application includes an ion transfer region whichincorporate means for controllably conveying ions from the ionisationregion, such as an ion guide. The ion transfer region is coupled to theionisation region.

Examples of ion guides include ion mobility, field asymmetric ionmobility and differential ion mobility, as well as DC, AC orradio-frequency driven stacked rings, monopoles, quadrupoles, hexapolesor octopoles. Guides may be used to transport ions in a DC or AC field,or some combination of fields. Certain AC or RF ion guides operate bycreating a ‘pseudo-potential well’ within which ions are stable. Someion guides may be operated to selectively transport ions of a certainm/z ratio, or range of ratios, and filter out all other ions. Preferablythe ion transfer region may be operated at ambient conditions forreasons of throughput, cost, complexity, efficiency and reliability.Examples of ion guides that may utilised at, or near, ambient pressureand temperature include ion mobility, field asymmetric ion mobility anddifferential ion mobility, as well high pressure RF ion guides such astransfer quadrupoles that exhibit collisional focussing of ions insidethe guide at partial vacuum pressures that are near atmosphericpressure. Thanks to the use of a pseudo-potential well in which the ionsmay be stably trapped without discharging on electrodes for longperiods, the operation may last over long periods of time, trapping ionsfor hours or even days.

Inside the ionisation region the input stream is ionised such thatcharge is lost or gains by means of oxidation or reduction at thepositive and negative electrodes respectively. More than one ionisationregion may be required to generate the primary ions necessary forcombination into the desired reaction product. Positive and negative ionsources may be needed. If we take the instance of the positive ionsource, neutral molecules lose charge to the positively chargedelectrode, or transfer charge to positively charged primary ions, andbecome positively charged ions. If primary ions are carefully selectedan ‘electrochemical series’ may be contrived between the primary ion andthe neutral molecule such that that the neutrals are preferentiallyionised in a desired configuration. Preferably the ionisation region isoperated under ambient conditions, so a desirable configuration utilisesan atmospheric ionisation technique e.g. corona discharge orelectrospray ionisation.

The ionization region is coupled to the ion transfer region. Ions aregenerated in the ionisation region and are drawn into the transferregion by means of a thermal gradient, a magnetic or electrical field,or by flow induced by a pressure differential. If more than oneionisation source is employed, they may be connected by means of an iontransfer region or regions. Ions are transported inside the transferregion by means of an ion guide or guides. In this way ions of oppositepolarity may be transferred for combination and neutralisation inside anion guide. Reaction products may be formed inside the ion guide andcollected as neutral molecules in the gas phase. Methods of collectingreaction products could include condensation, distillation, separationand purification of a vapour stream from the ion transfer region.

Electrodes of the ionisation source are connected via an externalcircuit to the poles of a power supply for operation. Charge lost to thepositive electrode flows as electric current through a circuit connectedto an oppositely charged electrode, or in the case of a system of thepresent application incorporating more than one ionisation region, to anoppositely (in this case negatively) charged ionisation source. Ifcharge transferred from the input stream exceeds the current drawn bythe ionisation source from a power supply, the circuit may be operatedas a fuel cell. To complete the circuit, however, ions must betransferred to an electrode of opposite polarity. In a conventional ionsource, ions are drawn to an oppositely-charged counter electrode insidethe source where they ground and complete the circuit. In an example ofthe present application, ions are transferred to oppositely chargedionization sources by means of an ion guide as described above.Therefore the ion guide operates in an analogous manner to theelectrolyte or membrane found in a classical fuel cell.

In an example of operation of the present application as a GTL device,methane is ionised in a first, positively charged ionisation source andwater is ionised in a second, negatively charged ionization source.Methane is non-polar, so preferably an atmospheric chemical ionization(APCI) source may be employed in the ionisation regions to generate thedesired molecular ions for subsequent transfer and combination. In oneexample of the present application an APCI utilises corona discharge togenerate positive or negative ions around a suitable field-concentratingelectrode, such as a needle. Similarly electrospray ionization may beused to generate ions from weakly polar compounds such as water.Positively charged CH+ ions and negatively charged OH− ions areconducted from the respective positive and negative ionisation sourcesvia an ion guide to combine into neutral methanol ions. Reactantproducts such as methanol may be collected from the exhaust of thedevice by means of condensation. Charge is conducted via an externallyconnected electrical circuit.

In an example of operation of the present application as a fuel cell,hydrogen is ionised in a first, positively charged ionization source andoxygen is ionisation in a second, negatively charged ionization source.In a preferred example an atmospheric pressure ionisation technique isemployed, one example of which is APCI. Positive H+ ions and negative O−ions are transferred from their respective sources by means of an ionguide inside an ion transfer region. The ion guide performs the functionof the membrane or electrolyte found in a classical fuel cell. Charge isconducted from the positive electrode of the first ion source via anexternally connected electrical circuit to the negative electrode of thesecond ion source. A load may be applied if the charge transferredexceeds the initial EMF required to prime the cell, and work may bedone.

In a preferred example the ionisation region is operated at atmosphericor near atmospheric pressure. Similarly, to reduce or eliminate theadditional complexity and power consumption of a vacuum pump, the iontransfer region, ion filter or ion guide is also operated atatmospheric, or near atmospheric, pressure.

Operation of the ion guide at higher pressure promotes condensation andprecipitation of liquids formed when sufficient numbers of neutralmolecules are generated during ion-ion and/or ion-molecule reactions.Examples of ion transfer techniques that operate at atmospheric, or nearatmospheric, pressure and based on DC and RF voltages include ionmobility spectrometry (IMS), high field ion mobility (HFIMS), drifttube, field asymmetric ion mobility (FAIMS), differential ion mobility,travelling wave ion guides, stacked ring ion guides, ion funnels, iontraps and monopole or multipole (quadrupole, hexapole or octopole) ionguides or structures for lossless ion mobility (SLIM) constructed fromat least one electrode.

An ion guide, ion filter, ion transport or ion transfer region that iseffective at these pressures will generally be operated at lower RFand/or DC voltages to prevent electrical discharge or breakdown betweenelectrodes. At lower voltages, the ion guide may be constructed from arange of smaller critical dimensions, for example with an inscribedradius of between 0.1 and 3.0 mm (cf. “Miniature Mass SpectrometerSystems Based on a Microengineered Quadrupole Filter”, AnalyticalChemistry 2010 and “A miniature mass spectrometer for liquidchromatography applications”, Rapid Communications in Mass Spectrometry,2011 and Syms R, Wright S, 2016, “MEMS Mass Spectrometers: the Next Waveof Miniaturization”, Journal of Micromechanics and Microengineering,Vol:26, for some relevant examples of microengineered ion guides and thedimensions of their electrodes) using miniature electrodes, and RFvoltages may be driven at higher frequencies. In these conditions, themean free path between collisions between ions and neutral molecules canbe shorter. More frequent collisions between charged particles andneutral molecules gives rise to collisional focussing within the ionguide which can improve transfer efficiency between ion guides, throughapertures and from ionisation regions.

A preferred means of constructing a miniature ion guide or ion transferregion is using microfabrication processes. The ion transfer device maybe constructed from printed circuit boards using lithography, or from asuitable insulating substrate such as plastic, silicon or ceramic usingmicromachining steps such as laser etching, chemical etching,electroplating, electroforming, anisotropic or isotropic etching andplasma etching and so on. The insulating substrate may be patterned andetched with suitable conducting material to generate miniatureelectrodes. When voltages are applied to these electrodes, provided theyare suitably insulated and electrically separated, electric fields arecreated that may be utilised to transfer ions generated at theionisation regions, and to transport, filter and react these ions withmolecules and/or ions generated at other ionisation regions. Manyexamples of micromachined, micro-electromechanical (MEMS) ormicrosystems devices existing including microfabricated ion guides, ionfilters, ion traps or ion transfer devices. The ion guide may beassembled from electrodes and other features microfabricated on planarsubstrates. The advantage of using such miniature devices is that theymay be readily scaled into massive parallel or serial arrays to improvethroughput. Thus for example, by using microengineered quadrupole ionguides a reasonably compact form is possible allowing for arrays to beco-formed which can increase yield and output. It will be appreciatedthat techniques for constructing such arrays would be well known to theperson skilled in the art, for example as evidenced by the very largeion guide array described in EP2058837A2, the entire contents of whichare incorporated herein by reference.

Processes possible include ion-molecule reactions include the ionisationof water and combination of hydroxyl ions (OH−) with methane moleculesto create methanol (or with ethane or butane to create ethanol orbutanol respectively), or the separate ionisation of water and methaneat the cathode and anode respectively to generate negative hydroxyl ionsand positive methane ions, and their combination in an ion-ion reactionto create methanol (or ethanol or butanol etc.). While these ion-ion andion-molecule reactions are possible in an ionisation region, they do notoccur selectively and therefore their reaction efficiency is limited.The addition of a selective ion transfer region, based on a suitable ionguide, trap or filter, is utilised to select the ‘starter’ ions forcombination with neutral molecules from a rich background, or other ions(which may have also been selected as starter ions) to generate thedesired reaction products. The desired ions may be selected in an ionguide by their mass to charge ratio, before being combined in a reactionarea either inside the ion guide or at the intersection of more than oneion guide.

The ionisation region, or regions, coupled with ion transfer regions,ion guides and/or ion traps may be integrated from microfabricatedcomponents and assembled into individual cells. These cells may then bestacked in parallel and scaled up into very large arrays depending onthe desired throughput, flow rates and power output. Key factors in theoverall efficiency will include the ionisation efficiency of theionisation regions, the transmission efficiency of the ion transferregions (taking into account coupling between these regions), theefficiency of the selected ion-ion or ion-molecule reactions and thecollection efficiency of the condensed reaction products.

In one example of the present application at least one ionisation regionis coupled with at least one ion transport region for manipulation andcontrol of reactions of ions with surfaces, ions or molecules. Theionisation region generates charged particles or ions from startermaterials or fuels such as natural gas, air and water. The natural gasmay contain methane, ethane, butane and heavier hydrocarbon moleculesprior to ionisation in the ionisation region to form molecular ions.

The ionisation region may be based on a soft ionisation technique suchas glow discharge or electrospray ionisation to form molecular productions either directly or by charge transfer. The advantage of using ‘softionisation’ such as electrospray or glow discharge ionisation is thationisation efficiency is increased so boosting overall efficiency.

These product ions may be coupled into an ion transport or manipulationregion and conveyed to a reaction region for combination with other ionsor neutral molecules. The ions may be filtered and selected by the massto charge ratio within the ion manipulation region. The ion manipulationregion may include a trap to collect ions prior to introduction of a gasbearing neutral molecules for ion molecule reactions to generate thedesired reaction products. The trap may be a quadrupole, rectilinear,linear, toroidal or cylindrical ion trap or some other ion trap tocollect and filter ions for reaction. Alternatively the ion manipulationregion may rely on a technique operating at higher pressures, i.e. closeto, just below or at, ambient pressure rather than at vacuum, totransport, select and finally reaction ions at atmospheric pressure orhigher such as ion mobility, differential ion mobility, structures forlossless ion transport or travelling wave or some other ion mobilitysection. Ideally, the ion manipulation region operates at higherpressures, for example between 1×10⁻³ and 760 Torr, to reduce pumpingrequirements, power consumption and complexity (cf., “MEMS MassSpectrometers: the Next Wave of Miniaturization”, Syms R, Journal ofMicromechanics and Microengineering, Vol:26 2016 for some relevantexamples of miniaturized ion guides and their operating conditions). Asecond ionisation region may be included to produce ions from water,oxygen or some other fuel or starter materials. These ions may includehydroxyl ions or other functional groups that may be combined withmolecular ions generated from hydrocarbon starter materials in the firstionisation region to generate desired reaction products such as ethanol,butanol etc. via ion-ion reactions in the ion manipulation region. Theions generated in each ionisation region are coupled into the ionmanipulation region using suitable, low loss ion optics with an iontransmission efficiency of 1% to more than 70% such as an ion guide,Brubaker lens, electrostatic lens, einzel lens, stacked rings, starkelectrodes, cylinder lens or ion funnel. Similar, flow of a carrier gasthat is inert or unlikely to react with the ions generated in theionisation regions may be employed to propel them into the ionmanipulation region. The ions from at least one ionisation region arecombined in ion-ion reactions inside an ion guide, trap, pseudopotentialwell or reactor where they combine and, once they are neutralised,condense for collection at the bottom or walls or outlet of the reactionvessel. The ions may be filtered prior to combination using massanalysers, filters or traps, or intermediate reaction products may beselected for reaction to form the desired reaction products. Similarly,ions may be filtered and reacted with neutral molecules, or withreactive surfaces, or with ions, surfaces and neutrals in a series ofreactions to build more complex molecules with greater functionality.

Discharging ions on the opposite electrode of an ionisation region ofopposite polarity release charge and form current flow in an externalcircuit. The ions may be selected in the ion manipulation region andtransported to the opposite polarity electrode of the second ionisationregion. In this fashion the ion manipulation region or ion transportregion functions as a membrane in a fuel cell. In one example of thepresent application functioning as a fuel cell, positive or protonatedions which, in their simplest form are positively charged hydrogen ions,are generated at a first ionisation region. Positive ions lose charge tothe positive electrode of the ionisation region. This charge flows viaan external circuit connected via some load to the negative electrode ofthe second ionisation region. These positive ions are coupled with asecond ionisation region of opposite polarity via an ion manipulationregion. The ion transport or manipulation region may be capable ofselection of ions by mass to charge ratio to the exclusion of allothers. In one example the ion transporter is a miniaturised quadrupolemass analyser that can operate in RF-only mode to transport all ions, orwith a DC component in selected ion mode (SIM) to permit ions of a givenmass to charge ratio. A quadrupole assembled from microfabricatedelectrodes may operate at higher pressure, lower RF voltage and higherfrequency. If lengthened, the frequency can drop along with the voltageaccordingly. The ion transport region conveys positive ions from thepositive electrode of the first source to the negative electrode of thesecond source where they discharge on impact with the negativeelectrode, or via charge transfer, and complete the circuit. Increasedflow of fuel to the two ionisation regions ought to increase ion currenttransmitted through the ion guide between them, thereby increasingcurrent in the external circuit to a level capable of performing work.Again, transmission efficiency between ionisation regions via an ionguide will be critical, so coupling of ionisation regions with the iontransporting region relies on low-loss ion optics such as RF-only ionguides, pre-filters, hexapoles, quadrupoles, octopoles, ion mobility,drift tubes, travelling wave ion guides, stacked ring ion guides or someother low-loss, or lossless, ion transport mechanism.

Hence the system of the present application is capable of operating asan energy conversion system that functions as a fuel cell and generateselectrical current from a fuel or fuels, or as a reactor for conversionof starter materials into more complex molecules through ion-ion andion-molecules and which may preferably be adapted to operate as a gas toliquid process. The system of the present application ionises at leastone fuel or starter material and manipulates, selects and transportsions for reaction by means of suitable electrostatic or electrodynamicion guides, filters or drift tubes. The system of the presentapplication replaces the electrolyte, catalyst and/or membrane found inclassic fuel cells or GTL processes with an electrostatic orelectrodynamic ion manipulation region such as an ion guide, analyser,drift tube or filter.

These and other features will be better understood with reference to thefollowing drawings which provide the person of skill with anunderstanding of the present teaching but in no way is intended to limitthe present teaching.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application will now be described with reference to theaccompanying drawings in which:

FIG. 1 shows a schematic of the system of the present application.

FIG. 2 shows a schematic of the system of the present applicationoperating as a fuel cell including ionisation regions and an iontransport region.

FIG. 3 shows a schematic of the system of the present applicationoperating as a gas to liquid conversion process including ionisationregions and an ion transport region.

FIG. 4 shows a schematic of the system of the present applicationoperating as a gas to liquid conversion process including ionisationregions and an array of ion transportation devices.

FIG. 5 shows a schematic diagram of the method of the presentapplication.

DETAILED DESCRIPTION

The system of the present application is described with reference to theFIGS. 1 through 4 . The system may operation as a fuel cell or asprocess for converting gases to more complex molecules through theaddition of different functional groups in ion-ion and ion-moleculereactions. The system may form a module that may be scaled or stacked,or assembled into very large arrays (arrays of 10×10 cells or greater)to scale its power output, our liquid output, depending on its mode ofoperation.

FIG. 1 is a schematic of the system of the present application includingits primary regions, a first ionisation region 101, an ion manipulationregion 102 and a second ionisation region 103. A least one fuel orstarter material 104 and 106 is shown entering ionisation regions 101and 103 respectively. When the system of the present application isoperated as a fuel cell the ionisation regions 101 and 103 include ionsources that have opposite polarity.

These fuels or starter materials are ionised inside regions 101 and 103,preferably using a soft ionisation technique to generate a molecular, orpseudo-molecular ion. The ionization region 101 or 103 is preferablyoperated at ambient conditions (e.g. atmospheric pressure andtemperature) for reasons of throughput, cost, complexity and efficiency.Examples of suitable pressure ionisation techniques include electrosprayionisation, microspray, nanospray ionisation, photoionisation, laserionisation, field effect ionisation, electron impact, glow dischargeionisation, secondary ionisation, charge transfer and corona dischargeionisation or any other ionisation technique that generates ions formanipulation within the device of the present application. These ionsare coupled into an ion manipulation region 102 using suitable ionoptics. Preferably these ion optics are efficient at ambient conditions.The ion manipulation region 102 is also preferably capable of operationat ambient conditions and may be composed of suitable ion guides,filters, analysers or drift tubes. The ion manipulation region 102conveys ions from ionisation region 101 into region 103 to complete acircuit linking electrodes of opposite polarity inside regions 101 and103. Charge moves through an external circuit 107 to power load 105. Thesystem of FIG. 1 is a module that may be stacked or assembled inparallel or in series into very large arrays to scale its power output.

The method of the present application is described with reference toFIG. 5 . The method for energy conversion comprises: generating 501 ionsfrom respective input streams of starting material in at least one firstionisation region and at least one second ionisation region; conveying502 generated ions in at least one ion manipulation region from one orboth of the at least one first ionisation region and the at least onesecond ionisation region to facilitate a reaction between the generatedions of the respective streams; and filtering 503 the generated ions inat least one ion guide of the ion manipulation region. The ions may thenreact with other ions or neutral species at step 504.

FIG. 2 is a schematic of the system of the present application operatingas an energy conversion system, preferably a fuel cell. In this mode ofoperation a fuel enters 204 a first ionisation region 201 as an inputstream. This fuel 204 is preferably, but not limited to, methane but maybe another suitable fuel such as hydrogen, ethane, butane, pentane or analcohol such as methanol or ethanol. A second fuel 206 enters a secondionisation region 203 as an input stream. This second fuel 206 ispreferably, but not limited to, oxygen. In FIG. 2 methane, oxygen andtheir respective ion products are included for illustrative reasonsonly. These fuels could alternatively be hydrogen and oxygen, or ethaneand oxygen etc. These fuels are ionised at ion sources 207 and 208 whichinclude electrodes that are at opposite polarity. The ion sources 207and 208 preferably rely on, but are not limited to, soft ionisationtechniques such as electrospray, corona discharge, glow dischargeionisation etc. If the fuel 204 is a non-polar compound such as ahydrocarbon like methane, then an atmospheric pressure, soft ionisationtechnique such as corona discharge ionisation may be preferred for ionsource 207. A positive ion is generated at 207 and transmitted into ionmanipulation region 202. To optimise transmission suitable ion optics209 and 211 may be employed to efficiently couple ions from 201 into 202and 203 respectively. These ion optics 209 and 211 may be designed tohave maximum acceptance to couple the species ionised at 207 or 208 into202. Some examples of suitable ion optics with greater acceptanceinclude, but are not limited to, RF-only ion guides, RF-only quadrupolepre-filters, Einzel lens, cylinder lens, stacked ring electrodes, ionfunnels, hexapoles, octopoles and monopoles. Inside ion manipulationregion 202 is an ion guide or transporter 210 to convey ions from 201via 202 into 203, or from 201 and 203 into 202, where they gain chargefrom oppositely charged ions generated at 208. The ion guide 210 may becapable of filtering ions by their mobility, drift time, acceleration,cross section, diameter and/or mass to charge ratio, so that onlycertain ions are transmitted. This ion transporter 210 may be a massanalyser or ion mobility spectrometer capable of selecting or separatingions such as a drift tube, FAIMS, HFIMS, SLIM, quadrupole mass analyser,ion trap, quadrupole ion trap, cylindrical ion trap, toroidal ion trapor rectilinear ion trap.

Preferably ion transporter 210, and optics 209 and 211, may be operatedat ambient conditions to reduce system complexity, pumping requirementsand voltages. Transmission of ions from 201 and 203 for combinationinside 202, or from 201 through 202 for combination in 203, completescircuit 212 and provides current flow to power load 205. Likewise,positive ions from source 207 may be transported through 209, 210 and211 for neutralisation at 208, or negative ions from 203 may be conveyedto 207 for discharge and completions of external circuit 212. The keyfeature is the potential for selective transmission of certain ionsthrough 202 using ion filter 210. In this manner the need for aselective membrane that passes protons, or a catalytic surface, or anelectrolyte is eliminated and the system of the present application mayoperate reliably for long periods of time without coating, clogging,charging, crystallisation or degrading of critical components. Thesystem of FIG. 2 is a module that may be combined with other modules inseries or parallel to form large arrays and scale-up power output. Thesources 207 and 208 may be arrayed to increase ionisation and throughputof fuel, and increase ion current through 209, 210 and 211 andultimately current flowing through external circuit 212 driving load205.

FIG. 3 is a schematic of the system of the present application inoperation as a reactor rather than an energy conversion system,preferably as a gas to liquid process. Starter materials 304 and 306enter at least one ionisation region 301 and/or 303 as input streams.Methane and water are shown purely for illustrative purposes and may besubstituted with other compounds to generate reaction products ofgreater complexity and functionality than methanol as shown here. Thestarter materials are ionised in at least one ionisation source 307 and308 respectively. It should be noted that in the system of the presentapplication only one of the two ionisation regions may be necessary togenerate ions which perform ion-molecule in 302, rather than the ion-ionreactions in 302 that are shown here. Ions generated at 307 and 308 aretransferred into 302 via ion optics 309 and 311 respectively. Ion optics309 and 311 are designed to maximise transmission efficiency from the atleast one ionisation region 301 and/or 303 into ion manipulation region302 The ion optics are designed such that their acceptance angle ismaximised and coupled from one region to a second region is optimisedand may be based on a RF-only ion guide, pre-filter, stacked ringelectrode, SLIM, drift tube, HFIMS, FAIMS, Einzel lens, travelling waveion guide, electrostatic lens or electrodynamic lens. The ionmanipulation region 302 includes and ion transporter 310 which conveysor propels ions from ion optics 309 and 311 for reaction, combination,neutralisation or activation inside 310. The ion transporter 310 may besingular or plural and may also have the ability to select, filter orseparate ions by characteristics such as mass to charge ratio, mobility,drift time, time of flight, cross sectional area (CSA) or diameter suchas a mass analyser, quadrupole mass analyser, ion trap, quadrupole iontrap, rectilinear ion trap, linear ion trap, toroidal ion trap, magneticsector etc. Numerous examples of miniaturised or microfabricated ionoptical and filtering devices are known in the art. Electrode structuresmay be combined to generate a pseudopotential well when RF voltages areapplied, efficiently focussing and transporting ions from one end of anion guide to its exit. RF ion guides include stacked rings, ion funnels,quadrupoles, hexapoles and octopoles. The ionisation regions 301 and303, and the ion manipulation region 302, are preferentially operated atambient pressure and temperature to reduce system complexity, expense,cost, size and power consumption. The sources 307 and 308, the optics309 and 311, and the transporter 310 may all be miniaturised ormicrofabricated from metal shim electrodes, planar electrodes, MEMS orprinted circuit board assemblies wherein the electrodes formelectrostatic or electrodynamic focussing, filtering or separatingfields and the electrodes are spaced by suitable insulating materials.The ions generated from at least one source are focussed and ifnecessary filtered prior to combination or reaction with neutralmolecules or other ions to form the desired reaction product orproducts. In an exemplary embodiment methane and water are startermaterials which are ionised in respective ionisation regions,transported and selected for combination inside 311 to condense asmethanol for collection in 302. A power source is provided at 305 todrive the ion sources 307 and 308 and ionise starter materials 304 and305 as they are fed into regions 301 and 303.

FIG. 4 illustrates the reaction system of FIG. 3 wherein the ionmanipulation region 402 comprises a plurality of ion optics 409 and 411and ion transporters 410 to scale-up the throughput of starter ions into411 generating greater output of product for condensation andcollection. Microfabricated arrays of electrostatic and electrodynamicion optics, Brubaker lens and filters are known in the art.

Similarly sources 407 and 408 may be arrayed to increase ion current andionisation efficiency of greater flow of starter materials 404 and 406.Starter materials 404 and 406 enter at least one ionisation region 401and/or 403 as input streams Preferably the system in FIG. 4 is operatedat atmospheric or near atmospheric pressure and temperature. The outputproducts from 402 may be in turn an input stream and starter materialinto a further system of FIG. 4 for combination with another startermaterial to form more complex molecules with other functional groups. Inan exemplary embodiment methane and water are combined to form methanol,which in turn may be combined with other starter materials to formwaxes, paraffin and other heavier molecules. These modules of FIG. 4 maybe combined in series or parallel to scale-up output. A power source isprovided at 405 to drive the ion sources 407 and 408 and ionise startermaterials 404 and 405 as they are fed into regions 401 and 403.

It is not intended to limit the present teaching to any one set ofadvantages or features of the preferred example as modifications can bemade without departing from the present teaching.

Therefore, while exemplary arrangements have been described herein toassist in an understanding of the present teaching it will be understoodthat modifications can be made without departing from the scope of thepresent teaching. To that end it will be understood that the presentteaching should be construed as limited only insofar as is deemednecessary in the light of the claims that follow.

The invention claimed is:
 1. A gas to liquid conversion device forconverting at least one input stream to a liquid reaction product, thedevice comprising: a first ionisation region, the first ionisationregion comprising a plasma configured to generate ions from at least afirst input stream of starting material, the first input streamcomprising a gas; and at least one ion manipulation region for conveyinggenerated ions from the first ionisation region, the at least one ionmanipulation region comprising at least one ion guide for guiding thegenerated ions, the at least one ion manipulation region beingconfigured to facilitate at least one of an ion-ion or an ion-moleculereaction to effect generation of a condensed reaction product, thecondensed reaction product being output from the device as a liquid. 2.The device according to claim 1, comprising a second ionisation regionand wherein one or both of the first ionisation region and the secondionisation region are configured to provide a soft ionization ofstarting material.
 3. The device according to claim 2, wherein the softionisation is provided by one of the following: chemical ionisation,electrospray ionisation, microspray, nanospray ionisation,photoionisation, laser ionisation, field effect ionisation, electronimpact, plasma ionisation, glow discharge ionisation, secondaryionisation, charge transfer and corona discharge ionisation.
 4. Thedevice according to claim 1, wherein the at least one ion guidecomprises one of the following: mass analyser, ion mobilityspectrometer.
 5. The device according to claim 1, further comprising ionoptics for coupling the at least one ion manipulation region to thefirst ionisation region.
 6. The device according to claim 2, furthercomprising ion optics for coupling the at least one ion manipulationregion to the second ionisation region.
 7. The device according to claim6, wherein the ion optics comprises one of the following: RF-only ionguide, electrostatic lenses, einzel lens, stacked rings, cylinder lensor ion funnel, pre-filters, hexapoles, quadrupoles, octopoles, ionmobility, drift tubes, travelling wave ion guides, stacked ring ionguides, bunching optics or Stark decelerators.
 8. The device accordingto claim 1, further comprising a trap in the ion manipulation region fortrapping the generated ions.
 9. The device according to claim 8, whereinthe trap comprises one of the following: quadrupole, rectilinear,linear, toroidal or cylindrical ion trap.
 10. The device according toclaim 1, wherein the at least one ion guide further comprises an ionfilter for selectively transferring the generated ions according to oneor both of their mass to charge ratio and ion mobility.
 11. The deviceaccording to claim 2, wherein one or more of the at least one ionmanipulation region, the first ionisation region and the secondionisation region are constructed from microfabricated components. 12.The device according to claim 2, wherein the first ionisation region andthe second ionisation region are configured to have different voltages.13. A conversion system comprising an array of devices according toclaim
 1. 14. The device of claim 1, wherein the starting materialcomprises one of the following: methane, hydrogen, ethane, butane,pentane, methanol or ethanol.
 15. The device of claim 2, whereinstarting material for the first ionisation region comprises one of thefollowing: methane, hydrogen, ethane, butane, pentane, methanol orethanol and starting material for the second ionisation region comprisesone of the following: oxygen, air, water.
 16. The device according toclaim 1, configured to receive an input stream of a second startingmaterial.
 17. The device according to claim 16 wherein the input streamof the second starting material is coupled to a second ionisationregion, the second ionisation region configured to generate ions fromthe second starting material.